A sulfur-containing polycarbonate resin, its preparation method and application

Abstract

The present invention provides a sulfur-containing polycarbonate resin, a preparation method and an application thereof. The sulfur-containing polycarbonate resin comprises a structural unit represented by Formula I and a structural unit represented by Formula II. By introducing and matching the structural unit represented by Formula I and the structural unit represented by Formula II, the obtained sulfur-containing polycarbonate resin has the characteristics of high refractive index, low birefringence and excellent heat resistance while maintaining low yellowness and high light transmittance. At the same time, the preparation method is very simple and the raw material cost is low, which is very suitable for application in optical lenses.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a sulfur-containing polycarbonate resin, a preparation method thereof, and an application thereof. Background Art

[0002] Currently, the optical elements used in the optical systems of various cameras such as cameras, movie-in-one cameras, and video cameras include optical glass or transparent resins for optics. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and has various refractive indices (nD), Abbe values (ν D ), etc., but has high material costs, and problems of poor molding processability and low productivity. Optical transparent resins, especially optical lenses made of thermoplastic optical transparent resins, can be mass-produced by injection molding, and have the advantage of being easy to manufacture aspherical lenses.

[0003] Polycarbonate resin is one of the most commonly used optical transparent resins. Compared with ordinary polycarbonate, optical-grade carbonate copolymers should have a higher refractive index in order to achieve the same refraction effect under a smaller curvature and achieve the purpose of making the lens thinner and lighter; and ordinary polycarbonate has a relatively serious birefringence phenomenon. When used as an optical material, it is easy to produce phenomena such as delay, light leakage, and polarization loss. However, through the design of a special main chain structure, the optical-grade carbonate copolymer greatly reduces the generation of birefringence phenomenon, improves the light source utilization rate and the stability of optical information, and thus can prepare optical elements with better optical properties; in addition, the optical-grade carbonate copolymer also needs to have properties such as high light transmittance, high heat resistance, and high mechanical strength to meet the requirements of high precision and lightweight of high-end optical electronic products.

[0004] The industrialized polycarbonate is limited to bisphenol A polycarbonate. For example, CN103257376A discloses a method for preparing a low-birefringence polycarbonate resin by reacting 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, bisphenol A, and diphenyl carbonate. However, the highest refractive index of the polycarbonate resin prepared by this invention is only 1.639, and there is still a large room for improvement. Another example is that CN112961336A prepared a new derivative containing a fluorene skeleton structure by modifying 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and used it for polycarbonate synthesis to obtain a polycarbonate resin with a refractive index of up to around 1.7. However, the structure of the polycarbonate resin prepared by this invention contains a complex aromatic structure, is difficult to synthesize, and has a high preparation cost, making it difficult to effectively achieve industrial scale-up production.

[0005] Therefore, aiming at the above technical problems, developing a sulfur-containing polycarbonate resin with high light transmittance, low yellowness, and low birefringence phenomenon is still an urgent technical problem to be solved in this field. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a sulfur-containing polycarbonate resin, its preparation method and application. By introducing the structural unit shown in Formula I and the structural unit shown in Formula II in combination, the obtained sulfur-containing polycarbonate resin has the characteristics of high refractive index, low birefringence and excellent heat resistance while maintaining low yellowness and high light transmittance, and is suitable for application in optical lenses.

[0007] To achieve the purpose of this invention, the following technical solutions are adopted in the present invention:

[0008] In the first aspect, the present invention provides a sulfur-containing polycarbonate resin, which comprises the structural unit shown in Formula I and the structural unit shown in Formula II:

[0009] ;

[0010] In Formula I, X is selected from C1-C6 (such as C1, C2, C3, C4, C5 or C6) linear or branched alkylene groups;

[0011] R1 and R2 are each independently selected from any one of H, C1-C20 (such as C1, C3, C5, C9, C11, C13, C15, C17, C19 or C20, etc.) linear or branched alkyl groups, C1-C20 (such as C1, C3, C5, C9, C11, C13, C15, C17, C19 or C20, etc.) linear or branched alkoxy groups, C5-C20 (such as C5, C9, C11, C13, C15, C17, C19 or C20, etc.) cycloalkyl groups, C5-C20 (such as C5, C9, C11, C13, C15, C17, C19 or C20, etc.) cycloalkoxy groups, C6-C20 (such as C6, C9, C11, C13, C15, C17, C19 or C20, etc.) aryl groups, and C6-C20 (such as C6, C9, C11, C13, C15, C17, C19 or C20, etc.) aryloxy groups;

[0012] R3 and R4 are each independently selected from any one of H, C1-C20 (such as C1, C3, C5, C9, C11, C13, C15, C17, C19 or C20, etc.) linear or branched alkyl groups;

[0013] n is an integer from 0 to 5 (such as 0, 1, 2, 3, 4 or 5);

[0014] ;

[0015] In Formula II, Y is selected from C1-C6 (such as C1, C2, C3, C4, C5 or C6) linear or branched alkylene groups;

[0016] R5 and R6 are each independently selected from any one of H, C1-C20 (such as C1, C3, C5, C9, C11, C13, C15, C17, C19 or C20, etc.) linear or branched alkyl groups, C1-C20 (such as C1, C3, C5, C9, C11, C13, C15, C17, C19 or C20, etc.) linear or branched alkoxy groups, C5-C20 (such as C5, C9, C11, C13, C15, C17, C19 or C20, etc.) cycloalkyl groups, C5-C20 (such as C5, C9, C11, C13, C15, C17, C19 or C20, etc.) cycloalkoxy groups, C6-C20 (such as C6, C9, C11, C13, C15, C17, C19 or C20, etc.) aryl groups, and C6-C20 (such as C6, C9, C11, C13, C15, C17, C19 or C20, etc.) aryloxy groups;

[0017] L is a single bond or selected from , , , , , any one of them, where "*" represents the connection site, and R7, R8 and R 11 ~R 14 are each independently selected from any one of H, C1-C10 (such as C1, C3, C5, C7, C9 or C10, etc.) linear or branched alkyl groups, and C6-C10 (C6, C7, C8, C9 or C10) phenyl groups, and R9 and R 10 are each independently selected from any one of H, C1-C5 (C1, C2, C3, C4 or C5, etc.) linear or branched alkyl groups;

[0018] m is an integer from 0 to 5 (such as 0, 1, 2, 3, 4 or 5).

[0019] The sulfur-containing polycarbonate resin provided by the present invention comprises a structural unit shown in Formula I and a structural unit shown in Formula II; on the one hand, by introducing the structural unit shown in Formula I, since the weight per unit volume of the structure shown in Formula I is higher and it contains sulfur element, on the premise of ensuring a relatively small increase in the yellowness value of the obtained sulfur-containing polycarbonate resin, its refractive index can be effectively improved; on the other hand, since the structural unit shown in Formula I has negative birefringence and the structural unit shown in Formula II has positive birefringence, when the two are combined, while ensuring that the obtained sulfur-containing polycarbonate resin has a high refractive index, its birefringence phenomenon can be effectively reduced; in summary, by introducing and combining the structural unit shown in Formula I and the structural unit shown in Formula II, the obtained sulfur-containing polycarbonate resin has the characteristics of high refractive index, low birefringence and excellent heat resistance while maintaining low yellowness and high light transmittance, and is suitable for application in optical lenses.

[0020] Preferably, X is selected from methylene or ethylene.

[0021] Preferably, each of R1 and R2 is independently selected from any one of H, C1-C6 linear or branched alkyl, C1-C6 linear or branched alkoxy, C5-C10 cycloalkyl, C5-C10 cycloalkoxy, C6-C12 aryl, and C6-C12 aryloxy.

[0022] Preferably, each of R3 and R4 is independently selected from H or methyl.

[0023] Preferably, n is 0 or 1.

[0024] Preferably, the structural unit represented by Formula I is the structural unit represented by A1 or A2:

[0025] , .

[0026] Preferably, Y is selected from methylene or ethylene;

[0027] Preferably, each of R5 and R6 is independently selected from any one of H, C1-C6 linear or branched alkyl, C1-C6 linear or branched alkoxy, C5-C10 cycloalkyl, C5-C10 cycloalkoxy, C6-C12 aryl, and C6-C12 aryloxy.

[0028] Preferably, L is a single bond or is selected from any one of , wherein, "*" represents the connection site, each of R7 and R8 is independently selected from any one of H, C1-C10 linear or branched alkyl, and C6-C10 phenyl, and each of R9 and R 10 is independently selected from H, C1-C5 linear or branched alkyl.

[0029] Preferably, the structural unit represented by Formula II includes at least one of the structural units represented by B1-B4:

[0030] , , , .

[0031] Preferably, the molar percentage content of the structural unit shown in Formula I in the sulfur-containing polycarbonate resin is 5 to 80%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70% or 80%, etc., and more preferably 5 to 35%; by further limiting the molar percentage content of the structural unit shown in Formula I in the sulfur-containing polycarbonate resin, it can be ensured that the increase in the yellowness value of the obtained polycarbonate resin is relatively low without affecting the light transmittance of the polycarbonate resin.

[0032] In a second aspect, the present invention provides a method for preparing the sulfur-containing polycarbonate resin as described in the first aspect, and the preparation method includes: subjecting a dihydroxy compound having the structure shown in Formula III, a dihydroxy compound having the structure shown in Formula IV, and a carbonic acid diester to a polycondensation reaction to obtain the phosphorus-containing polycarbonate resin;

[0033] ;

[0034] In Formula III, X, R1 to R4, and n each independently have the same defined range as in Formula I;

[0035] ;

[0036] In Formula IV, Y, L, R5 to R6, and m each independently have the same defined range as in Formula II.

[0037] Preferably, the molar ratio of the sum of the dihydroxy compound having the structure shown in Formula III and the dihydroxy compound having the structure shown in Formula IV to the carbonic acid diester is 1:(1 to 1.1), such as 1:1, 1:1.02, 1:1.04, 1:1.06, 1:1.08 or 1:1.1, etc., and more preferably 1:(1 to 1.05).

[0038] Preferably, the dihydroxy compound having the structure shown in Formula III includes the compound shown as M1 or M2;

[0039] , .

[0040] Preferably, the dihydroxy compound having the structure shown in Formula IV includes any one or a combination of at least two of bisphenol A, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, or 4,4'-dihydroxybiphenyl.

[0041] Preferably, the carbonic acid diester includes any one or a combination of at least two of diphenyl carbonate, di(toluene) carbonate, di(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, or dicyclohexyl carbonate, and more preferably diphenyl carbonate.

[0042] Preferably, the polycondensation reaction is carried out in the presence of a basic catalyst.

[0043] Preferably, the molar ratio of the total of the dihydroxy compound having the structure shown in Formula III and the dihydroxy compound having the structure shown in Formula IV to the basic catalyst is 1:(10 -8 ~10 -3 ), for example, 1:10 -8 、1:10 -7 、1:10 -6 、1:10 -5 、1:10 -4 or 1:10 -3 etc., more preferably 1:(10 -6 ~10 -4 ).

[0044] Preferably, the basic catalyst includes any one or a combination of at least two of alkali metal compounds, alkaline earth metal compounds or nitrogen-containing compounds.

[0045] Preferably, the alkali metal compounds include any one or a combination of at least two of sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, or disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt or lithium salt of phenol.

[0046] Preferably, the alkaline earth metal compounds include any one or a combination of at least two of magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate or magnesium phenyl phosphate.

[0047] Preferably, the nitrogen-containing compounds include any one or a combination of at least two of quaternary ammonium hydroxide compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, imidazole compounds, ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate or tetraphenylammonium tetraphenylborate.

[0048] Preferably, the quaternary ammonium hydroxide compounds include any one or a combination of at least two of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or trimethylbenzylammonium hydroxide.

[0049] Preferably, the tertiary amine compound includes any one or a combination of at least two of triethylamine, dimethylbenzylamine, or triphenylamine.

[0050] Preferably, the secondary amine compound includes diethylamine and / or dibutylamine.

[0051] Preferably, the primary amine compound includes propylamine and / or butylamine.

[0052] Preferably, the imidazole compound includes any one or a combination of at least two of 2-methylimidazole, 2-phenylimidazole, or benzimidazole.

[0053] Preferably, the basic catalyst includes any one or a combination of at least two of lithium hydroxide, sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium bicarbonate, magnesium bicarbonate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium bicarbonate, calcium carbonate, cesium carbonate, strontium carbonate, barium carbonate, lithium acetate, sodium acetate, magnesium acetate, potassium acetate, calcium acetate, strontium acetate, barium acetate, sodium stearate, magnesium stearate, potassium stearate, calcium stearate, lithium benzoate, sodium benzoate, potassium benzoate, calcium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium phenyl phosphate, magnesium phenyl phosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, diethylamine, triethylamine, dimethylbenzylamine, triphenylamine, ammonium tetramethylborohydride, ammonium tetrabutylborohydride, ammonium tetrabutyltetraphenylborate, or ammonium tetraphenyltetraphenylborate.

[0054] As a preferred technical solution, the preparation method includes the following steps:

[0055] (1) Add the dihydroxy compound having the structure shown in Formula III, the dihydroxy compound having the structure shown in Formula IV, the dicarbonate, and the basic catalyst into a reaction kettle, and displace the air in the reaction kettle with nitrogen for 3 to 5 times to keep the pressure in the kettle at atmospheric pressure.

[0056] (2)First, heat the reaction kettle to 150 - 190 °C (such as 150 °C, 160 °C, 170 °C, 180 °C or 190 °C, etc.), react for 5 - 10 min (such as 5 min, 6 min, 7 min, 8 min, 9 min or 10 min, etc.), and then reduce the pressure in the reaction kettle to 15 - 35 kPa (such as 15 kPa, 17 kPa, 19 kPa, 21 kPa, 23 kPa, 25 kPa, 27 kPa, 29 kPa, 31 kPa, 33 kPa or 35 kPa, etc.), and react for 20 - 40 min (such as 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, 32 min, 34 min, 36 min, 38 min or 40 min, etc.);

[0057] (3)Then, heat the reaction kettle to 190 - 220 °C (such as 190 °C, 195 °C, 200 °C, 205 °C, 210 °C, 215 °C or 220 °C, etc.), reduce the pressure in the reaction kettle to 5 - 25 kPa (such as 5 kPa, 7 kPa, 9 kPa, 10 kPa, 15 kPa, 20 kPa or 25 kPa, etc.), and react for 10 - 30 min (such as 10 min, 13 min, 19 min, 20 min, 25 min or 30 min, etc.);

[0058] (4)Next, heat the reaction kettle to 220 - 250 °C (such as 220 °C, 225 °C, 230 °C, 235 °C, 240 °C, 245 °C or 250 °C, etc.), reduce the pressure in the reaction kettle to 1 - 5 kPa (such as 1 kPa, 2 kPa, 3 kPa, 4 kPa or 5 kPa, etc.), and react for 10 - 30 min (such as 10 min, 13 min, 19 min, 20 min, 25 min or 30 min, etc.);

[0059] (5)Finally, heat the reaction kettle to 250 - 290 °C (such as 250 °C, 255 °C, 260 °C, 270 °C, 280 °C or 290 °C, etc.), reduce the pressure in the reaction kettle to 0.1 - 1 kPa (such as 0.1 kPa, 0.2 kPa, 0.4 kPa, 0.6 kPa, 0.8 kPa or 1 kPa, etc.), and continue to react for 30 - 90 min (such as 30 min, 40 min, 50 min, 60 min, 70 min, 80 min or 90 min, etc.). After the reaction is completed, the sulfur - containing polycarbonate resin is obtained;

[0060] Preferably, the step (2) specifically includes: first, heating the reaction kettle to 165-175 °C and reacting for 5-10 min, and then reducing the pressure in the reaction kettle to 20-30 kPa and reacting for 25-35 min.

[0061] Preferably, the step (3) specifically includes: then heating the reaction kettle to 210-220 °C, reducing the pressure in the reaction kettle to 10-20 kPa, and reacting for 10-20 min.

[0062] Preferably, the step (4) specifically includes: then heating the reaction kettle to 230-240 °C, reducing the pressure in the reaction kettle to 1-5 kPa, and reacting for 15-25 min.

[0063] Preferably, the step (5) specifically includes: finally, heating the reaction kettle to 260-280 °C, reducing the pressure in the reaction kettle to 0.1-0.5 kPa, and continuing to react for 40-60 min. After the reaction is completed, the sulfur-containing polycarbonate resin is obtained.

[0064] In a third aspect, the present invention provides a polycarbonate resin composition, which includes the sulfur-containing polycarbonate resin as described in the first aspect and an additive.

[0065] Preferably, the additive includes any one or a combination of at least two of an antioxidant, a dye, a bluing agent, a flame retardant, a release agent, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a reinforcing agent, an antistatic agent, or an antibacterial agent.

[0066] In a fourth aspect, the present invention provides an application of the sulfur-containing polycarbonate resin as described in the first aspect or the polycarbonate resin composition as described in the third aspect in optical components, electronic products, or medical products.

[0067] Compared with the prior art, the present invention has the following beneficial effects:

[0068] The sulfur-containing polycarbonate resin provided by the present invention contains a structural unit shown in Formula I and a structural unit shown in Formula II; by introducing the structural unit shown in Formula I and the structural unit shown in Formula II in combination, the obtained sulfur-containing polycarbonate resin has the characteristics of high refractive index, low birefringence, and excellent heat resistance while maintaining low yellowness and high light transmittance. At the same time, the preparation method is very simple and the raw material cost is low, which is very suitable for application in optical lenses. Specific Embodiments

[0069] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0070] Unless otherwise specified, the raw materials involved in the following specific embodiments are conventional materials in the art and can be obtained through commercially available products or prepared according to existing methods.

[0071] The information of some raw materials involved in the following specific embodiments is as follows:

[0072] The structural formula of the dihydroxy compound M1 is: ;

[0073] The structural formula of the dihydroxy compound M2 is: .

[0074] Example 1

[0075] A sulfur-containing polycarbonate resin, which comprises a structural unit shown in A1 and a structural unit shown in B1;

[0076] ;

[0077] ;

[0078] The preparation method of the sulfur-containing polycarbonate resin provided in this example includes the following steps:

[0079] (1) At room temperature, 50.61 g (0.21 mol) of diphenyl carbonate, 13.70 (0.060 mol) of bisphenol A, 44.24 g (0.140 mol) of the dihydroxy compound M1, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide are added to the reactor, and the air in the reactor is replaced with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0080] (2) The temperature in the kettle is raised to 170 °C within 20 min, and the reaction is carried out for 10 min. Then, the pressure in the kettle is reduced to 25 kPa within 5 min, and the reaction is continued for 30 min;

[0081] (3) The temperature in the kettle is raised to 210 °C within 10 min, the pressure in the kettle is reduced to 15 kPa, and the reaction is carried out for 20 min;

[0082] (4) The temperature in the kettle is raised to 240 °C within 10 min, the pressure in the kettle is reduced to 5 kPa, and the reaction is carried out for 20 min;

[0083] (5) The temperature in the kettle is raised to 260 °C within 10 min, the pressure in the kettle is reduced to 0.1 kPa, and the reaction is continued for 60 min;

[0084] After the reaction is completed, stop heating, introduce nitrogen gas. After the temperature drops to room temperature, add an appropriate amount of tetrahydrofuran to dissolve the product, and precipitate and separate it in 1 L of anhydrous ethanol;

[0085] (7)Filter the precipitated polymer by suction, wash it several times with ethanol, and dry it under vacuum at 80 °C for 8 h to obtain the desired product.

[0086] Example 2

[0087] A sulfur-containing polycarbonate resin, which comprises a structural unit shown in A2 and a structural unit shown in B1;

[0088] ;

[0089] ;

[0090] The difference between the preparation method of the sulfur-containing polycarbonate resin provided in this example and that of Example 1 is as follows:

[0091] Step (1) is: at room temperature, adjust the raw material ratio to 50.61 g (0.21 mol) of diphenyl carbonate, 11.28 g (0.049 mol) of bisphenol A, 64.58 g (0.156 mol) of dihydroxy compound M2, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide, add them to the reactor, and displace the air in the reactor with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0092] The remaining steps refer to Example 1

[0093] Example 3

[0094] A sulfur-containing polycarbonate resin, which comprises a structural unit shown in A2, a structural unit shown in B1 and a structural unit shown in B2;

[0095] ;

[0096] ;

[0097] ;

[0098] The difference between the preparation method of the sulfur-containing polycarbonate resin provided in this example and that of Example 1 is as follows:

[0099] Step (1) is as follows: At room temperature, adjust the raw material ratio to 50.61 g (0.21 mol) of diphenyl carbonate, 10.92 g (0.048 mol) of bisphenol A, 18.23 g (0.042 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 49.27 g (0.119 mol) of dihydroxy compound M2, 1.6×10 -4 g of sodium hydroxide (4.00×10 -6 mol), add them to the reactor, and displace the air in the reactor with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0100] For the remaining steps, refer to Example 1.

[0101] Example 4

[0102] A sulfur-containing polycarbonate resin, which contains the structural units shown in A2, the structural units shown in B3, and the structural units shown in B4:

[0103] ;

[0104] ;

[0105] ;

[0106] The difference between the preparation method of the sulfur-containing polycarbonate resin provided in this example and that of Example 1 is as follows:

[0107] Step (1) is as follows: At room temperature, adjust the raw material ratio to 50.61 g (0.21 mol) of diphenyl carbonate, 5.59 g (0.03 mol) of 4,4'-dihydroxybiphenyl, 3.50 g (0.010 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 66.24 g (0.160 mol) of dihydroxy compound M2, 1.6×10 -4 g of sodium hydroxide (4.00×10 -6 mol), add them to the reactor, and displace the air in the reactor with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0108] For the remaining steps, refer to Example 1.

[0109] Example 5

[0110] A sulfur-containing polycarbonate resin, which contains the structural units shown in A2, the structural units shown in B1, and the structural units shown in B2:

[0111] ;

[0112] ;

[0113] ;

[0114] The preparation method of the sulfur-containing polycarbonate resin provided in this example is different from that in Example 1 as follows:

[0115] Step (1) is: at room temperature, adjust the raw material ratio to 50.61 g of diphenyl carbonate (0.21 mol), 9.13 g (0.040 mol) of bisphenol A, 42.10 g (0.096 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 26.50 g (0.064 mol) of dihydroxy compound M2, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide, add them to the reactor, and displace the air in the reactor with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0116] For the remaining steps, refer to Example 1.

[0117] Example 6

[0118] A sulfur-containing polycarbonate resin, which contains the structural unit shown in A2, the structural unit shown in B1, and the structural unit shown in B2:

[0119] ;

[0120] ;

[0121] ;

[0122] The preparation method of the sulfur-containing polycarbonate resin provided in this example is different from that in Example 1 as follows:

[0123] Step (1) is: at room temperature, adjust the raw material ratio to 50.61 g of diphenyl carbonate (0.21 mol), 7.76 g (0.034 mol) of bisphenol A, 57.88 g (0.132 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 14.08 g (0.034 mol) of dihydroxy compound M2, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide, add them to the reactor, and displace the air in the reactor with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0124] For the remaining steps, refer to Example 1.

[0125] Example 7

[0126] A sulfur-containing polycarbonate resin, which contains the structural unit shown in A1, the structural unit shown in B1, and the structural unit shown in B2:

[0127] ;

[0128] ;

[0129] ;

[0130] The preparation method of the sulfur-containing polycarbonate resin provided in this example is different from that of Example 1 as follows:

[0131] Step (1) is: at room temperature, adjust the raw material ratio to 50.61 g of diphenyl carbonate (0.21 mol), 11.41 g (0.050 mol) of bisphenol A, 30.70 g (0.070 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 33.12 g (0.080 mol) of dihydroxy compound M1, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide, add them to the reactor, and displace the air in the reactor with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0132] For the remaining steps, refer to Example 1.

[0133] Example 8

[0134] A sulfur-containing polycarbonate resin, which contains the structural units shown in A2, the structural units shown in B1, and the structural units shown in B2:

[0135] ;

[0136] ;

[0137] ;

[0138] The preparation method of the sulfur-containing polycarbonate resin provided in this example is different from that of Example 1 as follows:

[0139] Step (1) is: at room temperature, adjust the raw material ratio to 50.61 g of diphenyl carbonate (0.21 mol), 5.48 g (0.024 mol) of bisphenol A, 72.79 g (0.166 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 4.14 g (0.010 mol) of dihydroxy compound M2, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide, add them to the reactor, and displace the air in the reactor with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0140] For the remaining steps, refer to Example 1.

[0141] Example 9

[0142] A sulfur-containing polycarbonate resin, which comprises a structural unit represented by A2, a structural unit represented by B1, and a structural unit represented by B2:

[0143] ;

[0144] ;

[0145] ;

[0146] The preparation method of the sulfur-containing polycarbonate resin provided in this example is different from that of Example 1 as follows:

[0147] Step (1) is: at room temperature, adjust the raw material ratio to 50.61 g of diphenyl carbonate (0.21 mol), 9.13 g (0.040 mol) of bisphenol A, 66.13 g (0.151 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 3.73 g (0.009 mol) of dihydroxy compound M2, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide, add them into the reactor, and displace the air in the reactor with nitrogen for 5 times to keep the pressure in the kettle at atmospheric pressure;

[0148] For the remaining steps, refer to Example 1.

[0149] Example 10

[0150] A sulfur-containing polycarbonate resin, which comprises a structural unit represented by A2, a structural unit represented by B1, and a structural unit represented by B2:

[0151] ;

[0152] ;

[0153] ;

[0154] The preparation method of the sulfur-containing polycarbonate resin provided in this example is different from that of Example 1 as follows:

[0155] Step (1) is: at room temperature, adjust the raw material ratio to 50.61 g of diphenyl carbonate (0.21 mol), 0.68 g (0.003 mol) of bisphenol A, 2.19 g (0.005 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 79.49 g (0.192 mol) of dihydroxy compound M2, 1.6×10 -4g (4.00×10 -6 mol) of sodium hydroxide was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times to maintain the normal pressure in the kettle;

[0156] The remaining steps refer to Example 1.

[0157] Comparative Example 1

[0158] A polycarbonate resin comprising the structural unit shown in B1:

[0159] ;

[0160] The difference between the preparation method of the polycarbonate resin provided in this comparative example and that of Example 1 is as follows:

[0161] Step (1) was: at room temperature, the raw material ratio was adjusted to 50.61 g of diphenyl carbonate (0.21 mol), 45.66 g (0.20 mol) of bisphenol A, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times to maintain the normal pressure in the kettle;

[0162] The remaining steps refer to Example 1.

[0163] Comparative Example 2

[0164] A polycarbonate resin comprising the structural unit shown in B1 and the structural unit shown in B2:

[0165] ;

[0166] ;

[0167] The difference between the preparation method of the polycarbonate resin provided in this comparative example and that of Example 1 is as follows:

[0168] Step (1) was: at room temperature, the raw material ratio was adjusted to 50.61 g of diphenyl carbonate (0.21 mol), 22.83 g (0.10 mol) of bisphenol A, 43.85 g (0.10 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times to maintain the normal pressure in the kettle;

[0169] The remaining steps refer to Example 1.

[0170] Comparative Example 3

[0171] A sulfur-containing polycarbonate resin comprising a structural unit represented by A2:

[0172] ;

[0173] The difference between the preparation method of the polycarbonate resin provided in this comparative example and that of Example 1 is as follows:

[0174] Step (1) is: at room temperature, adjust the raw material ratio to 50.61 g of diphenyl carbonate (0.21 mol), 74.8 g (0.20 mol) of dihydroxy compound M2, 1.6×10 -4 g (4.00×10 -6 mol) of sodium hydroxide, add them to the reactor, and displace the air in the reactor with nitrogen 5 times to keep the pressure in the kettle at atmospheric pressure;

[0175] The remaining steps refer to Example 1.

[0176] Performance test:

[0177] (1) Glass transition temperature (Tg): Measured by dynamic differential thermal analysis (DSC) according to the method provided in ASTM E1356.

[0178] (2) Refractive index (nD): Mold the polycarbonate resin into a sample film with a thickness of 1 mm, and then measure the refractive index of the sample film at a wavelength of 589 nm at 25 °C using an Abbe refractometer.

[0179] (3) Birefringence: Mold the polycarbonate resin into a mold piece with a thickness of 1 mm and test it using an ellipsometer.

[0180] (4) Transmittance: Mold the polycarbonate resin into a sample film with a thickness of 0.1 mm and measure it using a haze meter according to the method provided in ASTM D1003.

[0181] (5) Yellowness index (YI): Mold the polycarbonate resin into a sample film with a thickness of 1 mm and measure it using a spectrophotometer according to the method provided in ASTM E313.

[0182] Test the polycarbonate resins provided in Examples 1 to 10 and Comparative Examples 1 to 3 according to the above test methods, and the test results are shown in Table 1;

[0183] Table 1

[0184]

[0185] It can be seen from the data in Table 1 that the sulfur-containing polycarbonate resins provided in Examples 1 to 10 have both high Tg, high refractive index, high transmittance, low birefringence and low yellowness;

[0186] Since the polycarbonate resins provided in Comparative Examples 1 to 2 do not contain the structural unit shown by Formula I, they have a lower refractive index and a higher birefringence.

[0187] Since the polycarbonate resin provided in Comparative Example 3 does not contain the structural unit shown by Formula II, it has a lower Tg, and both birefringence and yellowing are higher.

[0188] The applicant declares that the present invention illustrates a sulfur-containing polycarbonate resin, its preparation method and application through the above-mentioned embodiments. However, the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of the raw materials selected for the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A sulfur-containing polycarbonate resin, characterized in that The sulfur-containing polycarbonate resin comprises a structural unit represented by formula I and a structural unit represented by formula II: ； In formula I, X is selected from a C1~C6 straight or branched alkylene group; R1 and R2 are each independently selected from any one of H, C1~C20 straight or branched alkyl, C1~C20 straight or branched alkoxy, C5~C20 cycloalkyl, C5~C20 cycloalkoxy, C6~C20 aryl, and C6~C20 aryloxy; R3 and R4 are each independently selected from any one of H, C1~C20 straight chain or branched alkyl; n is an integer from 0 to 5; Formula II; The molar percentage of the structural unit represented by formula I in the sulfur-containing polycarbonate resin is 5-80%.

2. The sulfur-containing polycarbonate resin according to claim 1, characterized in that Said X is selected from methylene or ethylene; The R1 and R2 are each independently selected from any one of H, C1~C6 straight chain or branched alkyl, C1~C6 straight chain or branched alkoxy, C5~C10 cycloalkyl, C5~C10 cycloalkoxy, C6~C12 aryl, and C6~C12 aryloxy; Said R3 and R4 are each independently selected from H or methyl; The n is 0 or 1.

3. The sulfur-containing polycarbonate resin according to claim 2, characterized in that The structural unit shown in formula I is the structural unit shown in A1 or A2: 、 。 4. A preparation method, characterized in that: The preparation method is used to prepare the sulfur-containing polycarbonate resin according to any one of claims 1 to 3, and the preparation method comprises: subjecting a dihydroxy compound having a structure represented by formula III, bisphenol A and a carbonic acid diester to a condensation reaction to obtain the sulfur-containing polycarbonate resin; ； In Formula III, X, R1 to R4 and n each independently have the same defined ranges as in Formula I.

5. The preparation method according to claim 4, characterized in that: The molar ratio of the sum of the dihydroxy compound having the structure shown in formula III and bisphenol A to the carbonic acid diester is 1:(1-1.1).

6. A polycarbonate resin composition, characterized in that The polycarbonate resin composition comprises the sulfur-containing polycarbonate resin according to any one of claims 1 to 3 and an additive.

7. An application, characterized in that: The application includes using the polycarbonate resin composition according to claim 6 in optical parts, electronic products or medical products.

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